Acrylic esters of secondary alcohols



Patented July 27,1948 A.

UNl'l'ED STATES PATENT orrici-z ACRYLIC es'rsas or SECONDARY ALCOHOLS Chessle E. Rehberg. Glenside, and Charles H. Fisher, Ablngton, Pa., asslgnors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application July I, 1944, Serial No. 548,933

11 Claims. (Cl. 260-486) (Granted under the act or March a, 1883, as. amended April 80,1928; 310 o. a. 151) This application is made under the act of In order better to illustrate the practice of our March 8, 1883. as amended by the act of April invention, the following examples are given: 80. 1928. and the invention herein described, if patented. may be manufactured and used by or EXAM? I for the Government of the United States of White, CHL-CHCOOCHwHQZ America for governmental purposes without the payment to us of any royalty thereon. 2.0 moles (120 g.) of isopropanol. 6.0 moles (516 This invention relates to new and useful ester 8.) of methyl acrylate, 15 g. of hydroquinone and I of acrylic and substituted acrylic acids and meth- 1 cc. of sulfuric acid were mixed and heated to ods for their preparation. More particularly, it boiling in a flask attached to a fractionating relates to such esters wherein the acid is esterified umn. The column was operated under total rewithasecondary alcohol. flux until the temperature at the still-head An object of the present inventionisto provide opped to 62-63 C. The distillate was then new esters of acrylic acids. By "acrylic acids or r wn o ve y s o ly. t e pe atu e be t esters thereof, we mean acrylic acid itself and below 64 C. This distillate consisted of the alpha-substituted acrylic acids, such as methamethanol-methyl acrylate azeotrope. when no crylic, ethacrylic, chloroacrylic and similar acids. more methanol was produced. the xc ss m t yl A further object is to provide new and improved a-cl'ylate was ll d. f ll w d y he lsopr p resins and'polymers of th acrylic type A furacrylate. The latter boiled at ,108-1l0 C. and ther object is to provide practical and economical had 13073 and 0- The yield Wa methods for the preparation of acrylic esters 1 3'7 percent of the theoretical.

secondary alcohols and of polymers and comb!- mers of such esters. Other objects and advann tases of the invention will appear-from the fol- 3- -pe'ntyl acrylate, c1 1; :CHCOOCH(C H )'z lowing description, I

The alcoholysis method of preparing acrylic 1.0 mole (88 g.) of (I-pentanol, 6.0 moles (516 esters from lower-boiling acrylates-is well known. 8- of methyl acrylate, 15 g. of hydroquinone and However econdary a1coho]s as distinguished 1 c0. 01' sulfuric acid were caused to react as in from primary alcohols. are generally regarded as Example The a'pentyl acrylate was Obtained too sluggish or chemicall inert to react 80 in percent yield, boiled at 63 C- at mm. and

in an alcoholysis or esterlfication reaction at a had 1-4210 n rate which makes the reaction of practical value. The i readily P1Ymer1zed in mass, in w have discovered t although the alcoholw aqueous emulsion and in an organic solvent when i of prepari g acryli esters is slow warmed in the presence of a Catalyst, Such as an when the alcohol used is isoproply alcohol, the organic peroxide. The polymer was softbut tough simplest secondary alcohol, it is quite satisfactory and elastic- It was much stmngel" tougher} n for the preparation of the acrylic esters of higher, less c than the Polymer Prepared from the secondary alcohols and can be used with mod- 1501mm! y l' erate success even with isopropyl alcohol.

In order to achieve a satisfactory rate of alco 40 EXAMPLE In holysisand to cause the reaction to proceed virethy1 2 p'entwl acmlate V tually to completion. it is essential to remove the CH2:CHCOOCH CH3) CHZcHwHm lower alcohol as it is liberated in the reaction, to

use a suitable esterification catalyst, to use a suit- 2,0 moles 204 g of 4- eth 1-2- n ta 1 6.0

able polymerization inhibitor and to use an exmoles (516 g.) of methyl acrylate. 15 g. of hydrocessof the lower acrylic ester. when these conquinone and 1 cc. of sulfuric acid were treated as ditions are fulfilled, a very satisfactory .rate of described in Example I. There was thus obtained alcoholysis is obtained; in many instances being a yield of 95 percent of the theoretical amount of comparable to that obtained in alcoholysis with a i-methyi-Z-pentyl acrylate boiling at 71 C. at 29 primary alcohol. mm. and having No", 1.4220 nd d4, 0.8723. The

Buten-l 411-3 acrylate,

3 product readily polymerized as described in Example II to produce a strong, tough, elastic, rubbery polymer similar to polyethyl acrylate and much harder and tougher than that obtained from the isomeric n-hexyl acrylate.

ExAmrnr: IV Z-heptyl acrylate,

. CH2.'CHCOOCH(CH3) (CH2) 4CH1 By proceeding substantially as in Example I, 2-octyl acrylate was prepared in 80 percent yield from 2-octyl alcohol and methyl acrylate, using hydroquinone as a polymerization inhibitor and sulfuric acid as a catalyst.

The ester, which boiled at 79 C. at 5.4 mm.'

and had N 1.4312 and d4, 0.8754, readily polymerized as described in Example II to produce a soft, tacky, elastic polymer which, however, was harder and less tacky than the polymer of n-octyl acrylate.

EXAMPLE VI cyclohexyl acrylate HzC-CH:

CHuCHCOO-H H1 H2 Hi Cyciohexyl acrylate was prepared from cyclohexanol and methyl acrylate, using p-toluenesulfonic acidas a catalyst and hydroquinone as a polymerization inhibitor, the procedure being substantially the same as was described in Example I. The product was obtained in 93 percent yield as a liquid whose boiling point was 75 C. at 11 mm. and which had N 1.4578 and d4, 0.9742.

In marked contrast to n-hexyl acrylate, cyclohexyl acrylate produced a polymer which was tough, elastic, and non-tacky.

EXAMPLE VII p-methylcyclohexyl acrylate H2C-CH2 CH;:CHCOOH Horn Similarly to the cyclohexyl ester described in Example VI, p-methylcyclohexyl acrylate was prepared in 81 percent yield. It boiled at C. at 5.5 mm. pressure and had N 1.4550 and 114", 0.9528. Its polymer was similar to that of cyclohexyl acrylate.

EXAMPLE VIII 2.0 moles (144 g.) of buten-1-ol-3, 6.0 moles (5168.) of methyl acrylate, 10 g. of phenylene diamine and 5 g. of aluminum tert.-butoxide were mixed and refluxed as in Example I. When no fractionally distilled. The desired acrylate boiled at 71 C. at 97 mm. and had ,N 1.4283 and d4, 0.9120. Theyield was 3'7 percent of the theoretical, some of the product being lost through polymerization.

From the examples described above, it is apparent that the alcoholysis method of preparing the acrylic esters of secondary alcohols produces very satisfactory yields and has a wide field of applicability. Thus, in addition'to the particular alcohols used in the examples, various other alkyl, cycloalkyl, aralkyl, haloalkyl and olefinic secondary alcohols may be used. Also, in addition to the esters of acrylic acid, those of substituted acrylic acids such asmethacrylic, ethacrylic,

chloroacrylic and similar acids may be prepared by our process.

It will be understood by those skilled in the art that the details or the process may be varied considerably without departing from the spirit and scope of the invention. Thus, instead of the par ticular catalysts used in the above examples, other known esterlfication or ester interchange catalysts may be used, as for instance, other mineral acids, aryl sulfonic acids, metal alcoholates, and so forth. Likewise. other polymerization inhibitors may be used such as aryl amines, phenols. copper salts, sulfur, and so forth. Furthermore, other acrylic esters may be used as a starting material, as for instance, methyl or ethyl methacrylate, ethyl acrylate, methyl or ethyl esters of chloroacrylic acid, ethacrylic acid, and so forth. Also, the alcohol which is liberated in the reaction may be removed from the reaction mixture by other means, as for instance, by adding a suitable entraining agent, such as an aliphatic or aromatic hydrocarbon of suitable boiling point, to the reaction mixture and distilling the azeotrope.

The acrylic esters of secondary alcohols are especially valuable because they readily polymerize'to produceresins which are harder, tougher,

stronger and less tacky than the resins obtained by polymerizing the corresponding normal alkyl esters. This effect is enhanced still farther if the secondary alcohol has one or more branched chains in its molecular structure. By copolymerization with other suitable polymerizable compounds, very wide variation of the properties of the polymer may be achieved.

Having thus described our invention, we claim:

1. The process of preparing unsubstituted acrylic acid esters of secondary alcohols which comprises reactinga molar excess of a lower alkyl acrylate corresponding to the acrylic ester desired with a secondary noncyclic alcohol of the structure RCHOHR in which R and R are alkyl roups in the presence of an esteriflcation catalyst and a polymerization inhibitor, and removing the resulting lower alcohol as it is formed during the reaction in the form of an azeotrope of the lower alcohol inthe lower alkyl acrylate.

2. The process defined in claim 1 in which the lower alkyl acrylate is methyl acrylate.

3. The process defined in claim 1 in which the secondary alcohol corresponds to the formula: Rr-CHOH-R', where R and R are alkyl radicals at least one of which has a branched chain.

4. A process as in claim 1 in which an aluminum alcoholate and an amine are used as cata-'= lytic and inhibiting agents, respectively.

'5. The process of preparing unsubstituted acrylic acid esters of secondary alcohols which comprises reacting a molar excess of a loweralkyl acrylic acid ester corresponding totthe'acrylic v ester desired with a secondary noncyclic alcohol having the general formula Allryl-CHOH-R wherein R is selected from the group consisting of alkyl and alkenyl. in the presence of an esterification catalyst and a polymerization inhibitor, and removing the resulting lower alcohol as it is formed during the reaction in the form of an, azeotrope of the lower alcohol and the lower alkyl acrylate. a

6. The process as defined in claim 5 wherein the secondary alcohol has the general formula Alkyl-CHOHAlkeny1 'of about three of the ester to one of the alcohol,

the latter being of the formula alky1--CHOH-R, in which R is selected from the group consisting of alkyl and alkenyl, said mixture aiso containing an esterification catalyst and. a polymerization inhibitor, and distilling oil. an azeotropic mixture e oi. the resulting lower alcohol and the said lower alkyl ester, as the lower alcohol is formed in the reaction.

' 10. The process described in claim 9 in which the lower alkyl ester is methyl acrylate and the secondary non-cyclic alcohol is 3-pentanol.

11. The process described in claim 9 in which the lower alkyl ester is methyl acrylate and the secondary nonecyclic alcohol is 4-methyl-2-pentanol.

' CHESSIE E. REHBERG.

CHARLES H. FISHER.

REFERENCES CITED The iollowing references are of record in the file of this patent:

UNITED STATES PATENTS Number Name I Date r 2,117,349 Neher May 17, 1938 2,122,716 Graves July 5, 1938 2,129,663 Barrett Sept. 13, 1938' 2,129,666 Barrett et 9.1. Sept. 13, 1938 2,138,763 Graves Nov. 29, 1938 2,251,765 Sorenson Aug. '5, 1941 OTHER REFERENCES Rule et al., Jour. Chem Soc. ILondon) (1929),!86 2274. 

